s2noi2017 PEARSON'S KARD SOFT ACID BASE (HSAB) THEORY AGICHEMmISY 7 ae ce ° elo pasics §— f Organic” gy CsIRNET ae o e 9 ® Inorganic Bp Physical % TIT JEE AdiChemistry Home ( INORGANIC CHEMISTRY ( COORDINATION GHEMISTRY [ < Spinel structures I I “Trans effect > ] + Hard & Soft Acids & Bases (HSAB) Theory + Applications of HSAB Principle PEARSON'S HARD & SOFT ACIDS & BASES (HSAB) THEORY ) Hard and Soft Acids and Bases (HSAB) Theory is a qualitative concept introduced by Ralph Pearson to explain the stability of metal complexes and the mechanisms of their reactions. However it is possible to quantify this concept based on Klopman's FMO analysis using interactions between HOMO ‘and LUMO, According to this theory, the Lewis acids and bases can be further divided into hard or soft or border line types. Hard Lewis acids are characterized by small ionic radii, high positive charge, strongly solvated, empty orbitals in the valence shell and with high eneray LUMOs. Soft Lewis acids are characterized by large ionic radii, low positive charge, completely filled atomic orbitals and with low energy LUMOs. Hard Lewis bases are characterized by small ionic radii, strongly solvated, highly electronegative, weakly polarizable and with high energy HOMOs. Soft Lewis bases are characterized by large ionic radii, intermediate electronegativity, highly polarizable and with low energy HOMOs, ‘The Border line Lewis acids and bases have intermediate properties, Remember that it is not necessary for Lewis acid or base to possess all the properties to be classified as hard or soft or borderline, In short, Hard acids and bases are small and non-polarizable, whereas Soft acids and bases are larger and more polarizable HSAB Principle: According to HSAB concept, hard acids prefer binding to the hard bases to give jonic complexes, whereas the soft acids prefer binding to soft bases to give covalent complexes. * The large electronegativity differences between hard acids and hard bases give rise to strong Ionic interactions. * The electronegativities of soft acids and soft bases are almost same and hence have less onic interactions. ie, the interactions between them are more covalent. * The interactions between hard acid - soft base or soft acid - hard base are mostly polar covalent and tend to be more reactive or less stable. The polar covalent compounds readily form either more ionic or more covalent compounds if they are allowed to react. hpstwmw-adichemisty.comfinarganiclcachemsabyhard-sof-acid-base-theory html vas2noi2017 PEARSON'S KARD SOFT ACID BASE (HSAB) THEORY ‘According to FMO analysis, the interactions between acids and bases are controlled by the relative energies of the participating frontier molecular orbitals (FMO) I.e., HOMO and LUMO. CHARACTERISTICS OF HARD, SOFT & BORDERLINE ACIDS & BASES pe of Auypose CHARACTERISTICS EXAMPLES It Atomic centres of small lonic radii (<80 pm). i* High positive charge, '* Empty orbitals in their lvalence shells. Hard acids —_|* Low electronegativity ((0.7-1.6) and low lelectron affinity. * Likely to be strongly solvated M+ High eneray LUMO. I+, Lit, Nat, K*, Be®*, Mg?*, Ca?*, Sr?*, Sn2+ laR*, Ga2*, in3*, Cr+, Co?*, Fe¥*, 13+, La, Sit, Tit, zr, Th4*, vo?* , uo,?* IBeMe2, BF3, BCI, B(OR)3, AIMe3 Large radii (>90 pm). * Low or partial positive charge. ** Completely filled lorbitals in their valence shells. i Intermediate lelectronegativities (1.9- 2.5) '* Low energy LUMO's lwith large magnitude of LUMO coefficients. \soft acids Icut, Ag*, Aut, Ho*, Cs*, TY, Hg2* , Pd2*, Ca?* , pet IMetal atoms in zero oxidation states [Border line lacids Fe?" , co? Ni?*, Cu, Zn? , Pb? , B(CH)5, $02, NOt I* Small radii (around |120pm) & highly solvated i electronegative atomic centres (3.0-4.0). * Weakly polarizable. Difficult to be oxidized. it High eneray HOMO. lHard bases IH20, OH", F, CI’, CHyCOz-, P04, S042", COs", NO3", C04", IROH, RO", R20, NH3, RNH, NaH, * Large atoms (>170 lpm) with intermediate lelectronegativity (2.5- 3.0) * High polarizability M* Easily undergo loxidation. i* Low energy HOMO's lbut large magnitude HOMO coefficients. \Soft bases IRSH, RS", R2S, I", CN", SCNT, $203", R3P, RyAs (RO)5P, RNC, ICO, CHa, Cee, RH IBorder line lbases |Aniline, pyridine, Ns’, Br’, NO", S032, Np ( TAPPLIGATIONS OF HSAB PRINCIPLE ) In hydrogen bonding: The strong hydrogen bond is possible in cases of H20, NH3 and HF, since the donor atoms (F, O & N) are hard lewi bases and their interactions with partially positively charged H, which is a hard acid, are stronger. hpitwmw-adichemisty.comfinarganiclcachemnsabyhard-sof-acid-base-theory html 28s2noi2017 PEARSON'S KARD SOFT ACID BASE (HSAB) THEORY Linkage of ambi jands to metal atoms: The ambidentate ligand, SCN” can bind either by S end or N ‘end. The bonding mode can be determined by using HSAB principle. It bonds through sulfur atom (soft base) when bonded to Pt2*, a soft acid, However it bonds through nitrogen atom (a hard base) when linked to Cr3*, a hard acid. Site preference in organic reactions: RCOX is a hard acid and reacts with the nitrogen end of SCN’ jon to form an acy| isothiocyanate, x CHyCOX +SCN—™ Re(ONeS Whereas the softer methyl group bonds to the Sulfur atom and forms methyl thiocyanate. x CHaX + SCN’ ——> CH,SCN Inorganic reactions: HSAB principle is used to predict the outcome of some of the reactions. 1) The following reaction is possible because As is softer than P and I” is softer than F- AsFg+Plp ——> Ady +PFo Remember that both As and P are soft but relatively As Is softer. 2) The following reaction is possible since Mg?* is harder acid than Ba?* and 0? is harder base than S® Mg +BaQ ——> MgO + BaS Precipitation reactions: The softer acids like Ag*, Hg*, Hg2* etc., and border line acids like Fe2*, Ni2*, Cu2+, 2n2*, Pb?* etc., can be precipitated as sulfides from their aqueous solutions since S* ion is a softer base. [ = Spinel structures I I Tans effec > Author: Aditya vardhan Vutturi hpitwmw-adichemisty.comfinarganiclcachemnsabyhard-sof-acid-base-theory html a3